Preparation of epoxide resins



United States Patent PREPARATION OF Eroxmn RESlNS Stephen E. Freeman, Milwaukee, and Gordon W. Gottschalk, Port Washington, Wis, assignors to Freeman Chemical Corporation, a corporation of Wisconsin No Drawing. Application December 20, 1954 Serial No. 476,596

14 Claims. (Cl. 260-47) This invention relates to improvements in the preparation of epoxide resins.

The term, epoxide is herein intended to refer to resms which contain an epoxy group, that is, a group comprising an oxygen radical linked to two carbon atoms which are, in turn, linked to each other in some other Way, for example,

Generally, epoxide resins are made by the condensation of polyfunctional phenols such as dihydric phenols and either an epihalohydrin such as epichlorhydrin, or a dihalohydn'n such as glycerol dichlorhydrin.

These resins are useful in the manufacture of varnishes, molding resins, adhesives, fibers, films, etc.

The following procedure is illustrative of a conventional method of preparing epoxide resins:

A caustic soda solution is made containing 1 mol caustic soda per mol of bisphenol (p,pdihydroxydiphenyldimethyl methane) dissolved in an amount of water, e. g., twice the weight of the bisphenol used. The bisphenol is then added to the caustic solution in a reaction kettle and with the aid of heat and agitation the bisphenol is dissolved. Epichlorhydrin is then added to the solution at a temperature of 35-45 C. with continuous agitation of the reaction mixture. The temperature rises to about 60-75 C. in 30 minutes, depending on the initial temperature, the batch size and the amount of water used. Larger amounts of water can be used to control the exothermic reaction. After this preliminary reaction, an additional amount of sodium hydroxide in water solution sufiicient in amount together with that.

previously added to react completely with the chlorine of the epichlorhydrin, is added and heat applied if necessary to raise the temperature to around 80-85 C. over a period of 15-20 minutes. A further amount of sodium hydroxide is then added in water in excess of the theoretical amount required to react with all the chlorine present in the epichlorhydrin. This excess may be 15 to percent more than theoretically required. The mixture is then heated to around 95-100" C. for a sufficient time to produce the desired products, e. g., from A: hour to 3 hours.

The reactive mixture separates into an upper aqueous layer which is drawn oif and a tafly-like resin which.

settles to the bottom. Practically, it is not conveniently possible to draw off more than about 90 percent of the aqueous layer containing dissolved sodium hydroxide and sodium chloride due to entrainment of the resin in the water. The resin products are then washed by stirring with hot'water for -30 minutes and the wash water drained oif. This washing procedure is repeated 4 to dtimes or more to remove all the unreacted sodium hydroxide and the sodium chloride. It is also possible to incorporate the use of acid such as acetic or hydroohlo'ricinihe wash water to neutralize the excess caustic.

The last traces of caustic and of basic salts such as sodium acetate must be removed before the drying step to follow, since their presence may catalyze further polymerization of the resin to a gel at the temperatures used to dehydrate the resins. After thorough washing, the resin is heated with agitation to drive oif the residual water. This requires temperatures substantially above the boiling point of water to effect dehydration, e. g., up to 150 C.

Many resins, especially those useful in coating, have softening points of C. and higher. Without the use of pressure to obtain higher temperatures with the water system, resins with softening points higher than 95 C. cannot be produced by the method described above since it is impossible mechanically to agitate the mass.

In preparing these resins, it is essential to remove the alkali entirely in order to avoid undesirable polymerization either during the dehydration step or upon standing or aging. The neutralization of the alkali, of course, produces salts and the removal of these salts has presented an impracticable burden because of the vast quantitles of washing required. It has been suggested to dissolve the resin in acetone and after filtering to free it from Water and solvent, but this requires a great deal of solvent and has proved very costly.

Mere washing of the resin with water to remove alkali and salts is difiicult because of the high viscosity and tatfy-like character of the resin. If suitable contact is obtained by agitation, there is a tendency to lose resin by mechanical dispersion of the resin in the wash water. Furthermore, an agitator of considerable power is required because of the high viscosity of the resin.

In spite of the difficulties, standard procedure, up to the time of the present invention, has been to wash the resin repeatedly with hot water until all traces of residual alkali are removed, after which the water is removed by evaporation with heat.

These difliculties are avoided in the present invention in which the condensation reaction is carried through in the normal fashion up to and including the point where the aqueous solution is decanted from the resin so far as possible. At this point in the operation, a stripping liquid is added to the system, preferably in an amount sufficient to give about 20-50% of this volatile liquid in the reaction vessel.

The stripping liquid(s) should possess the following characteristics:

The stripping liquid should be capable of boiling in the presence of water thereby assisting in the removal of the water from the resin; the fluid should be substantially immiscible with the water at the temperature of the condensed liquids in the separator; the fluid should be capable of boiling either at atmospheric pressure or non-atmospheric pressure within the range of about 7l99 C., preferably about 8293.3 C.; and the fluid should not be capable of appreciable reaction with the resin or residual material, as exemplified by alkali(s) and/or salts. liquid is also a solvent for the resin, there is a reduction in the viscosity of the resin and the resulting intimacy of the contact of the liquid with the entrapped water in the resin is advantageous in conducting effective and economical water removal.

If desired, the stripping liquid may contain a modifier which is a relatively less active stripping liquid. This modifier reduces the amount of relatively active stripping liquid required and may serve to adjust the evapo ration rate of the resin system after the alkali(s), water and salts have been substantially removed. For example, the combination of a stripping liquid such as methyl ethyl ketone with a modifier or less active stripping liquid It has been found that if the stripping.

such as xylol would reduce the water-solubility of the 7 system quite satisfactorily.

" water-solutions; These; requirements eliminate the use;

of. esters, unless the system is neutralized bejoreadding a.

stripping liquid: Examples of' suitable esters areas follows: I

Ethyl acetate Isopropyl acetate- Secondary butyl acetate n-Butyl acetate Ethyl propionate A. practical consideration in selecting the stripping liquid isthat thedistillateshould form .(at least) atwo layer-con densate with water, one of which'is highiniwater-content and the otherof which is high inlstrippin-g liquid content.

V In carrying outthe invention a. stripping liquid such asa methyl isobutyl ketone isadded to theresin whichcontains mechanically held water'plus salts and a slight excess of alkaliwhich has not been neutralized, It ispreferred to neutralize the excess alkali with an acidjsuchas, diluted hydrochloric acid or any other acid whichdoes not afiect L the resin. Neutralization of this excess alkali tends. to obviate saponification of the stripping liguid and facilitatesfiltration of the precipitatedjsaltsfro njthe solution' -a t a later ge, .28. Will be discussed hereinafter.

The neutralized system isiheated in a closed vessel, and a mixture of water. andla stripping-liquid such as,

' methyl isobutyl ketone dist ills into a. condenser fitted with a separating system which allows the wat'er to separate and the stripping liquid to return tgthe kettle; During .the removal of the water, the boiling. point. is about 82 C.

; When most of the water has been distilled'ofi; the boiling a point of the system slowly rises. Theboiling point. of pure methyl'isohutyl ketone is about 1155 C.; the system ultimately reaches this temperature unless reduced pressure is appliedto the system;

It has been found that any temperature above about 99 C. is undesirable since it tends to accelerate the formation of polymer. Although satisfactory results are ob tained when the system is-operated at about 7l99 C., thepreferred rangeis about 82-933; C. g

As the boiling point begins to rise, the saltsin the system begin t-o precipitate. By'retaining the stripping liquidduring the entire operation, the viscosity of the resinisreduced which facilitates removal-0f the salts; Duringthe later stages of the distillation, welhave found it advantage'ous. toimpose' a partial vacuum to prevent the temperature from going above about 993' C; PreferablyQthe temperature is held within the range of about 82-933" C.

until all; the water hasbeen removed, althougha sstated above, a temperature range50f about; 71'.9-9?1C. is satisfactory.; f j V Order t maintainthe isti latimt ystem at aflge erally constant temperatureleve nfi l; beidcsirable to,

reduce. the pressurewithin the-system; For example iwhen the system is initiallyv started and thereafter-maintained to apply a reduced pressure (i. e.-vacuum), thus-enabling the'system to maintain its initial operating-temperature range.

Reduction of the temperature to below about 71 C. will produce a higher viscosity. For that reason, it is preferred not to go to too low a temperature. A lower viscosity can be reached at alower temperature provided the solids content is maintained low, but itis preferred to maintain a high solids content which is more adaptable to ater procedures andis more economical; Once the water has been removed; the salts andfany caustic soda present become insoluble and-precipitate-in finely divided form. By filtration through-paper, or. other filtering media, preferably With the use ofcommon filter aids, the salts and alkali maybe removed so completely as to be undetectable by theiuseof normal indicators.

Artest for determining their absence is to shake the resin solution violently with pure water, after which the water j is ste wi .pheno p halein fonalltali filldfsilvcr, nitr t for chloride. When properly filtered,negativemesults: h u d e: b n d thr othles s.

R ins y e prepar d. y h si cthod ransi sf rom h s containing 1 m l of isph nol t ;mplss f p chlor:

. y fio hus n a n n moi f isiihBnQL Q-JLZZ.

mols of epichlorhydrin. The reduction of viscosity; by v the solvent permits the use of ordinary agitators;

Resins with a ratio of lrnol of bisphenol to less than 1.22 mols of epichlorhydrin produce a greater viscosity v whichisto-o high fornormaltype agitators. However,

iffat that stage of the condensation and'water evaporation,

additional methyl isobutyl ketone or similar solvent is: added, the viscosity may bCTEdLlCEdftO permitflresinsof: the lowerfepichlorhydrincontent to be prepared; 7 a

It has been found that occasionally.ffiltrationtis rather.

I difiicult;-due,;apparently, to someunneutlralized finely 'divided alkali.

If; "the material isgthoroughlymeutralized; u tyj a ly a oi e Furthermore; complete neutralization results; in; a resin solution; whichis; stable on longstorage whereas even airace gQ'ff alkali tends to cause poly'rnerization on storage; Similarly,- if the-tern: perature is perrnitted to go substantially aboveaboflt 9.9; C. "during dehydratiomthe stability is lowered; j

Ifadesired, our improved method maybe employed in; preparing epoxide. resins resulting'from thereactionpf; (a) a polyfunctional phenol, such as a;dihydric-;pli en ol;; free from reactive groups other than phenolic hydroxyl roup a mp fi y isp e ol, s cinolz h 5;

hydroxynaphthalene with (b) either a n epil algl ydrn i 91 a Pi l rl v .0 v a halohy insuckaaslwemL i hl hy inv r a The; followingexamples serve to illustrate -v the presentinvention, but arenot to be regardedasIimitingJhe-jn V vention in any way:

' i no P S i may bansq t ary Qt. esi able! Example I e A caustic soda solution; was .prepared;..by; dissolving 13.15 pounds of sodiumihydroxide, in. IBM-pound of;

water in a reactionvvesseluequippedtwith, atrnechanicab stirrer, The .solution was then, heated to about 51.6"; C; and 53.60 pounds'.of,Bisphenol A were. addedtupon agi} tation, the Bispihenol ,A-dissolv'ed;- 26.60 p oundslof epiv chlorhydrin were then rapidly added. inaboutaone minute; period. The reaction mixture, was..agita ted;and,.,

about 20 minutes, thetemperature of thQICQCfiQIiAIIiXtllIC rose to about 93,3 96 Ch This;temperature .rangewasv maintained t'or about,401minutes (about 'Lhour. aftergthe additi n o ri hl hyd in) The r action.- mixtu e =Pa-.

rated intofan p r a ueo s lay r ch asdrannpf yik e inse j t eb ttom of e ea tion e s -.1

The resinous material was washedonce with near-boiling water and thewashed motherliquor wasagain decantedif 7 The washed resinwas neutralizedby slowly adding-0575;"

pound of concentrated hydrochloric acid1 1521 50}- incrernents while agitating the resinous-product; While agitation. was continued; 3010 pounds ofl-methyl i butyl ketone-were added to the .resin. Themeutralizdi system was heated in a closed vessel and a mixture of water and methyl isobutyl ketone distilled into a condenser fitted with a separating system which allowed the water to separate and the solvent to return to the kettle. During the removal of the water, the boiling point was around 82 C. When most of the water was distilled off, the boiling point of the system slowly rose and a partial vacuum was applied to the system in order to maintain the system at a temperature below about 99 C.; however, the system was kept at a temperature high enough (about 7l73.8 C.) to keep the resin in a fluid state. After all of the water had been removed, a filter aid was added to the resin (Dicalite 4200, diatomaceous earth). The resin (with the filter aid) was filtered in order to remove the solids and alkali. The filtered resin was adjusted to 70% total solids with methyl isobutyl ketone.

Example II In Example 1, supra, the upper aqueous layer was decanted from the reaction mixture and a talfy-like resin settled to the bottom of the reaction vessel. The resinous material was then washed once with near-boiling water. The washed mother liquor was decanted and the washed resin was neutralized with concentrated hydrochloric acid. In the instant example, the same general procedure was followed. However, the resinous material was not Washed with near-boiling water, but, instead, was treated directly with 2.45 pounds of concentrated hydrochloric acid. The omission of the hot water wash thus necessitated the use of a greater quantity of hydrochloric acid. The following weight materials were employed.

150.50 pounds of water 17.3 pounds of sodium hydroxide 51.60 pounds of Bisphenol A 31.30 pounds of epichlorhydrin 30 pounds or methyl isobutyl ketone 2.45 pounds of concentrated HCl Example 111 The same procedure was followed as set forth in Example I, however, the following weight materials were employed:

167.00 pounds of water 18.55 pounds of sodium hydroxide 47.10 pounds of Bisphenol A 38.3 pounds of epichlorhydrin 17.50 pounds of methyl isobutyl ketone 0.750 pounds of concentrated HCl An additional quantity of methyl isobutyl ketone (12.50 pounds) was added to the reaction mixture after the reaction mixture was neutralized with HCl.

Example IV The same procedure was followed as set forth in Example I, however, the following weight materials were employed:

88.90 pounds of water 10.22 pounds of sodium hydroxide 30.42 pounds of Bisphenol A 18.47 pounds of epichlorhydrin Stripping liquid:

8.83 pounds of xylol (less active stripping liquid or stripping liquid modifier) 8.83 pounds of methyl isobutyl ketone (stripping liquid) The final resinous product had a 70% total solids content. 8.22 pounds of Bisphenol A were added to this resinous reaction product. 0.94 pound of ethylene diamine (catalyst) in methyl isobutyl carbinol were added to the reaction mixture of the Bisphenol A and 70% solution of resin in methyl isobutyl ketone. The reaction mixture was then heated to about 1l0121 C. under reflux conditions until the resin became too heavy to agitate etfec- 6 tively. 4.53 pounds of xylol plus 4.53 pounds of methyl isobutyl ketone were added to dilute the mass in the kettle to about 60% total solids; heating was continued. The temperature was held at about 1l0-12l C. until the viscosity of W-Y (Gardner-Holdt scale) at 50% in 50:50 methyl isobutyl ketone-xylol solution was reached. The reaction mixture is then neutralized with a small amount of hypophosphorous acid. The neutralized reaction mixture was then refluxed to remove a trace of water (a portion of which may have been formed by the addition of hypophosphorous acid). The resinous product was then adjusted to 50% total solids with 11.39 pounds of Cellosolve acetate and 11.39 pounds of diacetone alcohol (thinners) Example V The same procedure was followed as set forth in Example I, however, the following weight materials were employed:

The secondary butyl acetate was added after neutralization with the HCl. The resinous product was adjusted to total solids by the addition of a thinner.

Example VI The same procedure was followed as set forth in Example I, however, the following weight materials were employed:

139.90 pounds of water 16.10 pounds of sodium hydroxide 47.90 pounds of Bisphenol A 29.02 pounds of epichlorhydrin 0.5 pounds of concentrated HCl 16.20 pounds of toluol The resinous product was adjusted to about 65% total solids content by the addition of 17.50 pounds of Cellosolve acetate and 1.30 pounds of toluol.

The present method which may leave the resin dis-- solved in the stripping liquid, if desired, is readily adaptable to the preparation of higher molecular weight epoxide resins from lower molecular weight types, as .il lustrated in Example 1V, supra. Heretofore, it has been essential to fuse the resin with a phenolic compound in order to accomplish this result, but by the present method, the operation may be carried out at the reflux. ing temperature of a stripping liquid such as methyl isobutyl ketone, particularly if a catalyst such as an amine is added. Ethylene diamine has been found to be particularly suitable for this purpose. Normally, less than 0.5% based on the whole solution is required for this purpose. It is possible by the use of such a catalyst to prepare a whole series of resins of increasing molecular weight and the process may even be carried considerably farther than with the fusion process because the molecular size is limited only by the solubility of the resin and the available solvents at the temperatures employed.

Stability of the ultimate product is obtained by neutralization with an acid. Hypophosphorous acid has been found to be particularly advantageous since it also contributes a bleaching action.

Amines have a tendency in some cases to cause an after-yellowing on baking of the resin film. Amines of the type shown in United States Patent No. 2,500,600 have less tendency to do this.

The phrase alkali-containing residual material is hereinafter intended to refer to residual matter (such as alkali ,metaLsalts, unreacted alkali, stic) which is present in the 'epoxide reaction product when the epoxjde resinis produced by reactingasuitable polyfunctionalphenol with either an epihalohydrin or dihalohydrin iuthe presence of alkali material.

a Theforegoing detailed description has been given for clearness of understanding only and no unnecessary limitations should be understood therefrom as modifications will be obvious to those skilled in the art.

We claim: 7 l. A-method of removing water from an'epoxide resin reaction product containing water, an'epoxide resin which,

is produced by the condensation of a l alohydrin and a polyfunctional phenol in the presence of caustic alkali,

- and remaining alkali-containing residual matter that is present after the epoxide is formed from said condensatioii reaction without necessitating further polymerization at a temperature of about 7l-99 Cl V 2. The method of claim 1 in which the distillation system is maintained at a temperature of about 71-99. C.

3. .The method of claim 1 in which the stripping liquid is a solvent for said resin and the distiliation system is maintained at a temperature of about 7l99 C.

4. Themethod'of claim 3 in which the stripping liquid 7 is a solvent for said resin and the distillation system is Q maintained at a substantially constant operating temperature within the range of about 7l99 CQ 5. The method of claim" 11 in which the reaction prodnot is neutralized prior to distillation and'the stripping liquid contains an ester, 7 V

6. The method of claim 1 in which aketone is used as astripping liquid. .v f r r 7. The method of claim 1 in which methyl isobutyl ketone is used as a strippingliquid. 1 e

8. The method of claim'l in which toluol-is used as a stripping liquid. s

and neutralized can I a of the'epoxide' resin to a gel, which'cornprises distilling Water from said reaction product, prior to the removal of residual matter from the epoxide resin, with the aid of a stripping liquid which boils from saidjreaction product temperature of about 71-99? C 9.-A method of removing water from an epoxide resin reaction product containing water, an epoxide resinproduced by the condensation ;of a halohydrin and a polyfunctional phenol in the presence of-caustic alkali, and remaining alkali-containing residual matter that is present af ter the epoxideis formed from said condensation re-i action Without necessitating further polymerization of the epoxide resin to a gel, which comprises distillingwater from said-reaction product, prior to the removal of restrippingliquid which boils from said'reaction product at a temperature of about 82-93.3 C,

'56 sidual matter from the epoxide'resin, with the aid of a V 18 s l0.;'I-fhe method of claim 9 in is a solvenflfor said; resin. and thefdistillation system is maintianed'at a temperature of about 82 93.3 C.

12. The method oflclaim 9 in which the strippingliquid is a solvent tor-said resin and the distillation system is maintained ,atja substantially constant operating ternperature within the range of about 82-'93.3 C. p

13; A methodof removing water from an epoxide resin reaction product containing water, an epoxide resin which is produced by the condensation of a halohydrin and,

polyfunctional phenol in the presence of caustic alkali, and remaining alkali-containing residual matter that is press t after the .epoxide isformed from said condensa tion reaction withoutfurther'polymerization of thetepoxide resin to a gel, which comprises distilling Water from H said reaction product, prior to the removal of residual matterfro'm the epoxide resin, with the aid-of'at least 20%{stripping' liquid, based on :they Weight ofsaid reaction product, whichboils from said reaction product at a temperature of about 71-99" C.

l4.- A method ofrernoving water from an epoxide resin reaction product containing water, an epoxide resin which isproduced bythe condensation of a halohydrin and polyfunctional phenol in the presence of caustiealkali',

and remaining alkali-containing residual matter that ;is

present after theepoxide is formed' from said condensation reaction withoutifurther polymerization of the epoxide resin to a'gel which comprises distilling Water'from' said reaction product, prior toithe removal of residual matter from the epoxide resin, with the aid of at least 35% stripping liquid, basedion the weight of said reaction product, which boils from ,said 'reaction product at a 7 References, Cited :in the; tile T this patent UNITED'STATES PATENTS 7 page 862. V

r which;the distillation systemis'rnaintained: at,a teinperature of about 7l99 C.; ll.v The method of claim 9 in which the stripping 'ligl i 

1. A METHOD OF REMOVING WATER FROM AN EPOXIDE RESIN REACTION PRODUCT CONTAINING WATER, AN EPOXIDE RESIN WHICH IS PRODUCED BY THE CONDENSATION OF A HALOHYDRIN AND A POLYFUNCTIONAL PHENOL IN THE PRESENCE OF CAUSTIC ALKALI, AND REMAINING ALKALI-CONTAINING RESIDUAL MATTER THAT IS PRESENT AFTER THE EPOXIDE IS FORMED FROM SAID CONDENSATION REACTION WITHOUT NECESSITATING FURTHER POLYMERIZATION OF THE EPOXIDE RESIN TO A GEL, WHICH COMPRISES DISTILLING WATER FROM SAID REACTION PRODUCT, PRIOR TO THE REMOVAL OF RESIDUAL MATTER FROM THE EPOXIDE RESIN, WITH THE AID OF A STRIPPING LIQUID WHICH BOILS FROM SAID REACTION PRODUCT AT A TEMPERATURE OF ABOUT 70-90*C. 